WO1988002417A1 - A method for the manufacture of products containing fibers of lignocellulosic material - Google Patents

A method for the manufacture of products containing fibers of lignocellulosic material Download PDF

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Publication number
WO1988002417A1
WO1988002417A1 PCT/SE1987/000445 SE8700445W WO8802417A1 WO 1988002417 A1 WO1988002417 A1 WO 1988002417A1 SE 8700445 W SE8700445 W SE 8700445W WO 8802417 A1 WO8802417 A1 WO 8802417A1
Authority
WO
WIPO (PCT)
Prior art keywords
lignin
solution
fiber
fixing
fibers
Prior art date
Application number
PCT/SE1987/000445
Other languages
English (en)
French (fr)
Inventor
Rune Simonson
Brita Ohlsson
Birgit ÖSTMAN
Original Assignee
Rune Simonson
Brita Ohlsson
Oestman Birgit
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rune Simonson, Brita Ohlsson, Oestman Birgit filed Critical Rune Simonson
Priority to AT87906636T priority Critical patent/ATE62949T1/de
Priority to BR8707832A priority patent/BR8707832A/pt
Priority to DE8787906636T priority patent/DE3769661D1/de
Publication of WO1988002417A1 publication Critical patent/WO1988002417A1/en
Priority to NO882426A priority patent/NO171568C/no
Priority to FI891559A priority patent/FI86268C/sv

Links

Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21JFIBREBOARD; MANUFACTURE OF ARTICLES FROM CELLULOSIC FIBROUS SUSPENSIONS OR FROM PAPIER-MACHE
    • D21J1/00Fibreboard
    • D21J1/08Impregnated or coated fibreboard
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/21Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/23Lignins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27NMANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00Manufacture of substantially flat articles, e.g. boards, from particles or fibres

Definitions

  • a method for the manufacture of products containing fibers of lignocellulosic -material is provided.
  • the present invention relates to a method for the manufacture of products containing fibers of lignocellu ⁇ losic material and which involves disintegration of a lignocellulosic material into fibers, forming and press ⁇ ing of the fiber web into the product in question.
  • the sensitivity of the fiberboard to moisture can be attributed to the fiber material.
  • the factors ob ⁇ structing the manufacture of moisture-resistant fiber products are thus primarily the moisture absorption property of the fibers, the resultant dimensional changes and the tendency of the fiberboard towards cracking and disintegration on repeated wetting and drying.
  • Another significant factor is the tendency of the fiber material to rot.
  • a treatment intended to improve dimensional stability and resistance to rotting should therefore aim at alterations in the fibers them ⁇ selves and not, primarily, in the fiberboard products.
  • the obstacle to manufacturing fiberboards which are dimensionally stabilized and resistant to rotting is overcome by executing the present invention, which is defined in that the lignocellulosic material that forms the fibers is impregnated with lignin in conjunc ⁇ tion with water and at a pH which does not substanti ⁇ ally exceed 12.5, and wherein said lignin, once it has been absorbed by the fibers, is fixed against leaching by water through the modification of same into an essen ⁇ tially water-insoluble form.
  • the present invention gives a method for the im ⁇ pregnation of fibers intended for the manufacture of fiber-based products, which produces a dimension stabi ⁇ lizing effect and a consequent reduction in cracking, and gives resistance to rot in an • economically bene ⁇ ficial process.
  • the substance used for impregnation in the method in accordance with the invention contains as its active ingredient essentially lignin, appropriately derived from the alkaline kraft cooking process for the manu ⁇ facture of paper pulp, i.e. waste liquor lignin.
  • lignin appropriately derived from the alkaline kraft cooking process for the manu ⁇ facture of paper pulp, i.e. waste liquor lignin.
  • SUBST alkali lignin is known to be produced in large amounts in the course of the manufacture of paper pulp in accordance with this chemical pulping process. Such lignin is available in large quantities and at a price which makes it attractive in this context.
  • the lignin .to be capable of being absorbed by the fibers in the method according to the invention it must be present in the form of an aqueous solution or an aqueous dispersion. Its liquid form thus renders it suitable for use in the established methods used for forming fiber-based products, e.g. fiber ⁇ boards. It is, of course, appropriate to use water in this case for reasons of cost. Nor does the process of board forming offer feasible alternatives, as the water interacts with the water used in the forming process step (wet-forming) or with the moisture present in the fiber on dry-forming.
  • the lignin which is only water-soluble to a limi ⁇ ted extent in the form in which it is received, but is soluble in an alkaline solution, can be transformed into a fully water-soluble form, e.g. by carboxymethy- lation.
  • the starting material is suitably kraft lignin (sulfate lignin) which has been precipitated by the •addition of an acid at, for example, pH 9 from the industrial waste liquor from the kraft cooking process.
  • the kraft lignin (sulfate lignin) is reacted in .an aqueous solution (for 10 h at 90 C) with NaOH and mono- chloroacetic acid in the mole ratio of 1:2:1, where the molecular mass for a C9-unit in the lignin is set to 200.
  • the carboxymethylated lignin is precipitated with acid at a pH of about 2 and is isolated by centrifuga- tion.
  • the lig ⁇ nin can be dissolved in acetic acid and subsequently reprecipitated.
  • the modification of the lignin into a water- soluble form can be carried out according to several aspects
  • SUBSTITUTE SHEET methods of introducing hydrophilic groups in the lig ⁇ nin In addition to carboxyme h lation, carboxyethyla- tion with chloropropionic -acid provides another way of achieving a generally termed carboxyalk lation.
  • Car- boxylation by oxidation e.g. with oxygen or air in accordance with the oxygen bleaching step used for paper pulp bleaching, can also be used, as well as sulfonation. Different methods of modifying the lignin can be used sequentially.
  • the impregnation with lignin required for use of the method according to the present invention can be performed as described below.
  • lignocellulo ⁇ sic material like wood chips is defibrated at high temperature (usually 120-170°C) in a disc defibrator equipped with one or two rotating discs.
  • the hot fiber pulp discharged from this defibration step has a dry content of 30-60%, and can suitably be directly trans ⁇ ported and immersed into the impregnating solution containing lignin, the solution having a temperature of 10-80 C. Excess impregnating solution can be drained or pressed off from the- fiber material. It is essential for good results that the fibers be thoroughly impreg ⁇ nated with the solution.
  • the amount of lignin added to the fiber pulp can be adjusted by regulating the lignin concentration in the impregnating solution.
  • the lignin can also be added to the fiber pulp such that the lignin-containing impregnating solution is sprayed or sprinkled over the fiber pulp, for example at the pas ⁇ sage of the fiber pulp through the so-called blow-line used for transportation of the fibers from the disc refiner (beater) .
  • the lignin has, as mentioned, a limited solubility in water, but it can be added to the fiber pulp in that state in a soluble form by making the impregnating solution alkaline, the pH being substantially below 12.5.
  • the impregnating solu ⁇ tion penetrates into the fiber material in such a way that impregnation is obtained.
  • the lignin in its at least partially water-soluble form, is susceptible to leaching in water and in this state the material is not suitable for use in those applications for which it is primarily intended, i.e. out of doors. It is according ⁇ ly necessary to fix the lignin by transforming it into a water-insoluble form.
  • This can be achieved by treat ⁇ ing the fiber material in a second step with an aqueous solution of metal salts such as aluminum salt, copper salt or a mixture of aluminum and copper salt, respec ⁇ tively. Even used in small amounts, copper provides additional protection- against rot.
  • the combination of lignin and copper affords excellent resistance to white rot and brown rot fungi, and also to soft rot fungi and tunnelling bacteria from non-sterile soil.
  • the fixing is generally intended to be performed by the addition of metal salt as ⁇ stated above, this does not prevent the fixing solution, at least in some cases, from being an acidic solution with no metal salts.
  • the fixing step can be performed in different ways depending on the intended method of forming the fiber ⁇ boards.
  • the fiber pulp can, after the excess of
  • iUBS lTUTfc impregnating solution containing lignin has been removed by pressing or drainage, be furnished with an aqueous solution containing e.g. aluminum salt, to achieve fixing.
  • Excess fixing solution can be removed in a second drainage or pressing step, before the fiber material is further treated in accordance with an established method for the forming of fiberboard.
  • the fixing solution preferably aluminum salt (possibly in combination with copper salt)
  • the fixing solution preferably aluminum salt (possibly in combination with copper salt)
  • the fixing solution preferably aluminum salt (possibly in combination with copper salt)
  • Another variant of the method according to the invention for manufacturing * of lignin-impregnated fiber material is to impregnate the lignocellulosic material, e. g. wood chips, chippings or shavings, with a lignin solution before the material is disintegrated to fibers in a disc beater (defibrator) . If the material is not defibred before the impregnation but is still in the form of chips, chippings or shavings, great care must be taken in terms of the uptake of impregnating lignin solution by the material, e.g. by increasing the time of exposure between the material and the solution.
  • the lignocellulosic material e. g. wood chips, chippings or shavings
  • the fixing of the lignin material can suitably be carried out in a step following the defibration/refin ⁇ ing.
  • the aqueous solution of lignin should not be excessively alkaline (pH max. 12.5). This makes it easier to achieve good results. By avoiding the use of an excessively alkaline solution, the inherent
  • the fixing solution is provided in an appropriate form by using a weakly acidic solution, which improves the fixing effect by facilitating the chemical process which transforms the lignin into its water-insoluble form.
  • a weakly acidic solution which improves the fixing effect by facilitating the chemical process which transforms the lignin into its water-insoluble form.
  • metal salts e.g. aluminum salt
  • a rela ⁇ tively large quantity of metal ions is required, and the quantity increases in step with the increase in the quantity of lignin used in impregnation.
  • the quantity of metal ions required is greater than that provided by the copper required for the aforementioned additional pro ⁇ tection against rot.
  • the fiber material owing to its small particle size and disintegrated form, is comparatively easy to impregnate. Favourable penetration conditions may therefore be expected. In many cases it is thus possible to avoid having to take special measures, such as achieving complete solubility in water, to increase penetration.
  • the temperature of the heat treatment must be at least 80 G, and preferably 110 C, for a good reaction to take ' place.
  • the heat treatment can suitably be carried out in conjunction with the pressing and drying of the fiber board at a high temperature (usu ⁇ ally 200-250°C) .
  • fixing by heat can be carried out by adding ammonia and/or ammonium salt to the impregna ⁇ ting solution containing lignin, allowing the fixing to be carried out in a second step in which the fiber material is heated to a temperature of at least 80 C.
  • This heating step is preferably carried out in conjunc ⁇ tion with the drying of the fiber material to low moisture content before pressing and/or in conjunction with pressing into the consolidated product.
  • the modi- fication of the lignin into a water-insoluble form is thereby achieved by a chemical reaction between the fiber material and the lignin material.
  • the presence of a balanced amount of copper results in increased - resistance to rotting.
  • Such an addition can also take place when heat fixing is used.
  • the fiber material is then supplied with copper, preferably by impregnating the fibers with an aqueous solution of a copper salt.
  • a copper salt preferably by impregnating the fibers with an aqueous solution of a copper salt.
  • zinc can be used, in which case the impregnation is carried out with a solution containing a zinc salt.
  • the amounts of metal salts required do not need to be as high as if the fixing was performed merely by the addition of metal salt. Instead, the order of magnitude required is the same as that to achieve the additional protection against rot.
  • the fixing action in this case is achieved by the heat treatment itself.
  • the forming of the final product, usually board products, from impregnated fibers can be done by well-known, established methods. Two different methods can be distinguished, namely wet-forming and dry-forming.
  • the fibers are suspended in the water used for the forming process, the stock dilution water or furnish water, and the fiber suspension . is transferred to the endless wire (net) of the wet lap forming machine. The suspension is dewatered on the wire net. The fibers are then pressed together, between usually cold rollers, and the product is finally pres ⁇ sed in a heated press. The fibers in the final product are held together by the adhesion which results from the pressing of the fiber material. Adhesives (glue) can also be used.
  • a layer of the fiber material with a given moisture content, usually max. 10%, is arranged in a press, and the final product is formed by press ⁇ ing.
  • the fibers are held together by adhesion, but the binding of the fibers is usually reinforced by the addition of adhesives (glue) .
  • the impregnation of the fibers in the method according to the invention is always carried out before the forming takes place.
  • the fixing of the lignin can be done in the fiber before the forming step, or in conjunction with the forming by addition of the fixing solution to the stock dilution water.
  • the lignin can be fixed before the forming is executed. The forming should then be done before the fiber material has dried after the fixing, since the material requires a certain moisture content in the pressing.
  • the impregnation according to the invention can be per ⁇ formed by different, alternative routes.
  • the raw mate ⁇ rial might be any lignocellulosic material.
  • the final products are, as stated, fiber products, mainly fiber ⁇ boards (board products) .
  • Step 1 Washing of the material (e. g. wood chips) , preheating.
  • the impregnating" solution which is drained off can be recirculated to step 3.
  • the fixing solution drained can be recircula ⁇ ted to step 5.
  • Step 1 Washing of the material (e. g. wood chips), preheating.
  • the impregnating solution which is drained off can be recirculated to step 3.
  • Steps 5 and 6 can suitably be carried' ' out together, on preparation of the fiber stock solution (fiber suspension) , by adding the substances necessary for the fixing accord ⁇ ing to step 6 to the stock dilution water used in step 5.
  • Step 1 Washing of the material (e. g. wood chips), preheating.
  • the impregnating solution which is drained off can be recirculated to step 2.
  • Fixing by addition of fixing solution like aluminum (and possibly copper) salt solution.
  • the fixing solution drained can be recircula ⁇ ted to step 5.
  • Step 1 Washing of the material (e. g. wood chips) , preheating.
  • the impregnating solution which is drained off can be recirculated to step 2.
  • Steps 5 and 6 can suitably be carried out together, on preparation of the fiber stock solution (fiber suspension) , by adding the substances necessary for the fixing accord ⁇ ing to step 6 to the stock dilution water used in step 5.
  • Step 1 Washing of the material (e. g. wood chips), preheating.
  • the impregnating solution which is drained off can be recirculated to step 3.
  • Step 1 Washing of the material (e. g. wood chips), preheating.
  • the impregnating solution which is drained off can be recirculated to step 2.
  • Example 1 Fiber pulp used for manufacturing of fiberboard was steamed with water vapor at 100 C and then immersed in a room-temperature water solution containing fractionated kraft lignin (sulfate lignin) .
  • the pH value of the impregnating solution was about pH 11.
  • the procedure given above was carried out at two different concentrations of lignin in the impregnating solution: 15 and 5%.
  • the sheets were post-treated with heat, heat treating, for 4 hrs at 165°C.
  • Controls were prepared in the same way and from the same raw material except that no lignin impregna ⁇ tion and no fixing were performed.
  • Example 2 Fiber pulp was treated as in Example 1, except that the impregnation with lignin was performed with a water-soluble, carboxymethylated kraft lignin.
  • the pH-value of the impregnating solution was 7.5 and the concentration of lignin was about 10%.
  • the fixing was done in accordance with Example 1.
  • the test results are given in Table 1 (sample C) .
  • Example 3 In order to study the effect of a simul ⁇ taneous attack of different rot fungi such as white, brown and soft rot fungi as well as of tunnelling bac ⁇ teria, wood samples impregnated to different contents of lignin and copper, respectively, were exposed to unsterile soil in a fungus cellar. The results, found after a exposure time of 9.5 months, are given in Table 2. As can be seen from the table, all samples (except untreated controls) showed good results, even those samples which were impregnated to a low lignin content. Table 1. Test results obtained for lignin-impregnated fiber building boards (density 1000 kg/m )

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  • Dry Formation Of Fiberboard And The Like (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Paper (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)
  • Compounds Of Unknown Constitution (AREA)
PCT/SE1987/000445 1986-10-03 1987-10-01 A method for the manufacture of products containing fibers of lignocellulosic material WO1988002417A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
AT87906636T ATE62949T1 (de) 1986-10-03 1987-10-01 Verfahren zur herstellung von lignocellulosefasern enthaltenden erzeugnissen.
BR8707832A BR8707832A (pt) 1986-10-03 1987-10-01 Processo para a fabricacao de produtos contendo fibras de material lignocelulosico
DE8787906636T DE3769661D1 (de) 1986-10-03 1987-10-01 Verfahren zur herstellung von lignocellulosefasern enthaltenden erzeugnissen.
NO882426A NO171568C (no) 1986-10-03 1988-06-02 Fremgangsmaate for fremstilling av produkter som inneholder fibre av lignocellulosemateriale
FI891559A FI86268C (sv) 1986-10-03 1989-03-31 Förfarande för framställning av lignocellulosamaterialfibrer innehålla nde produkter

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE8604212-4 1986-10-03
SE8604212A SE455001B (sv) 1986-10-03 1986-10-03 Forfarande vid tillverkning av produkter innehallande trefibrer

Publications (1)

Publication Number Publication Date
WO1988002417A1 true WO1988002417A1 (en) 1988-04-07

Family

ID=20365814

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SE1987/000445 WO1988002417A1 (en) 1986-10-03 1987-10-01 A method for the manufacture of products containing fibers of lignocellulosic material

Country Status (11)

Country Link
US (1) US5100511A (sv)
EP (1) EP0328533B1 (sv)
JP (1) JPH02500039A (sv)
AU (1) AU606893B2 (sv)
BR (1) BR8707832A (sv)
ES (1) ES2005026A6 (sv)
FI (1) FI86268C (sv)
PT (1) PT85864B (sv)
RU (1) RU1806240C (sv)
SE (1) SE455001B (sv)
WO (1) WO1988002417A1 (sv)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4133445A1 (de) * 1991-10-09 1993-04-15 Fraunhofer Ges Forschung Verfahren zur herstellung von holzspanplatten und mitteldichten holzfaserplatten
WO1993018227A1 (en) * 1992-03-13 1993-09-16 Casco Nobel Ab Process for making board
EP0355094B1 (en) * 1987-03-09 1995-07-19 Metsä-Serla Oy Procedure for manufacturing lignocellulosic material products
DE19647240A1 (de) * 1996-11-15 1998-05-28 Hofa Homann Gmbh & Co Kg Holzfaserplatte und Verfahren zu ihrer Herstellung
WO1998035800A1 (en) * 1997-02-14 1998-08-20 Cellutech, Llc Method of forming ligno-cellulosic composite particle products with lignin as an adhesive

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU757773B2 (en) * 1997-11-26 2003-03-06 Sds Biotech K.K. Method for the treatment of wood with metallic treatment and wood treated by the method
MY135208A (en) * 2003-03-31 2008-02-29 Matsushita Electric Works Ltd A method of producing a fiber board
DE102004050278A1 (de) * 2004-10-14 2006-04-27 Basf Ag Helle bis weiße Holzwerkstoffplatten
JP2009500189A (ja) * 2005-06-29 2009-01-08 ビーエーエスエフ ソシエタス・ヨーロピア 明色の木質材料板
US9850623B2 (en) 2014-11-26 2017-12-26 Sally KRIGSTIN Water, grease and heat resistant bio-based products and method of making same
FR3120206A1 (fr) * 2021-03-01 2022-09-02 Sas Woodoo Procede de fabrication d’un materiau composite ligno-cellulosique et materiau composite obtenu par ce procede
CN113878683B (zh) * 2021-10-27 2022-05-03 东北林业大学 一种高力学强度、透光、耐水的全木质基光热转换薄膜及其制备方法

Citations (1)

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NO50613A (sv) *

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CA743861A (en) * 1966-10-04 Dansk Spaanplade Kompagni A/S Manufacture of chipboard and the like
US1873056A (en) * 1931-11-25 1932-08-23 Armstrong Cork Co Manufacture of fibrous articles
US1988231A (en) * 1932-11-09 1935-01-15 Crown Willamette Paper Company Copperized pear wrap paper
US2037522A (en) * 1933-03-01 1936-04-14 Mo Och Domsjo Wallboard Compan Hard board and method of making same
US2332369A (en) * 1941-09-27 1943-10-19 Minnesota & Ontario Paper Co Method of making low density water resisting fibrous products
US2470764A (en) * 1943-09-23 1949-05-24 Dunbar Thomas Leonidas Method of treating waste sulfite liquor
US2731344A (en) * 1953-05-11 1956-01-17 Ralph H Mckee Process for making pulp and paper
US3236720A (en) * 1960-04-14 1966-02-22 Dow Chemical Co Method for increasing flexural strength of paper
US3403074A (en) * 1965-05-11 1968-09-24 Emerite Corp Process of impregnating wet board with sulfite lignin liquor and acid
US3305435A (en) * 1966-07-07 1967-02-21 Weyerhaeuser Co Method of making paper stiffened with waste pulp liquor solids
US4191610A (en) * 1975-04-09 1980-03-04 Prior Eric S Upgrading waste paper by treatment with sulfite waste liquor
SE447554B (sv) * 1985-04-04 1986-11-24 Simonson Rune G W Forfarande vid tillverkning av produkter innehallande trespan

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
NO50613A (sv) *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0355094B1 (en) * 1987-03-09 1995-07-19 Metsä-Serla Oy Procedure for manufacturing lignocellulosic material products
DE4133445A1 (de) * 1991-10-09 1993-04-15 Fraunhofer Ges Forschung Verfahren zur herstellung von holzspanplatten und mitteldichten holzfaserplatten
WO1993018227A1 (en) * 1992-03-13 1993-09-16 Casco Nobel Ab Process for making board
AU665817B2 (en) * 1992-03-13 1996-01-18 Casco Nobel Ab Process for making board
DE19647240A1 (de) * 1996-11-15 1998-05-28 Hofa Homann Gmbh & Co Kg Holzfaserplatte und Verfahren zu ihrer Herstellung
DE19647240B4 (de) * 1996-11-15 2005-06-09 Fritz Homann Gmbh & Co. Kg Holzfaserplatte und Verfahren zu ihrer Herstellung
US5955023A (en) * 1996-11-27 1999-09-21 Callutech, Llc Method of forming composite particle products
WO1998035800A1 (en) * 1997-02-14 1998-08-20 Cellutech, Llc Method of forming ligno-cellulosic composite particle products with lignin as an adhesive

Also Published As

Publication number Publication date
FI86268C (sv) 1992-08-10
SE455001B (sv) 1988-06-13
AU606893B2 (en) 1991-02-21
SE8604212D0 (sv) 1986-10-03
US5100511A (en) 1992-03-31
RU1806240C (ru) 1993-03-30
AU8036387A (en) 1988-04-21
FI891559A (fi) 1989-03-31
BR8707832A (pt) 1989-10-03
EP0328533B1 (en) 1991-04-24
FI86268B (fi) 1992-04-30
PT85864A (en) 1987-11-01
ES2005026A6 (es) 1989-02-16
FI891559A0 (fi) 1989-03-31
EP0328533A1 (en) 1989-08-23
SE8604212L (sv) 1988-04-04
JPH02500039A (ja) 1990-01-11
PT85864B (pt) 1990-07-31

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